CN110295073A - Methane purification membrane bioreactor and its application method - Google Patents
Methane purification membrane bioreactor and its application method Download PDFInfo
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
Methane purification membrane bioreactor and its application method, it is related to a kind of methane purification reactor and its application method.The invention aims to solve the problem of that the energy and equipment investment demand are high and there is pollution environment during existing methane purification.Methane purification membrane bioreactor includes water feed apparatus, hydrogen feeder, biogas feeder, reactor, circulator and outlet liquid seal device.Application method: one, startup stage: methane purification biological medium being injected in reactor body, until methane purification biological medium liquid level reaches at reflux unit water outlet position, is passed through nitrogen, is sealed, and inoculation biogas purifies seed liquor；It opens hydrogen pressure reducing valve, biogas pressure reducing valve and circulating pump and carries out methane purification；Two, continuous running phases: every operation 12h closes 1 hydrogen pressure reducing valve, biogas pressure reducing valve and circulating pump, opens 1 intake pump.Advantage: bio-natural gas purity reaches 93% or more, and alcohol yied reaches 1.5g/Ld.
Description
Technical field
The present invention relates to a kind of methane purification reactor and its application methods.
Background technique
With world population it is continuous growth, it is industrialized increasingly developed, the demand to the energy constantly expands, and leads to the whole world
Fossil fuel reserves are increasingly reduced, while combustion of fossil fuel discharges a large amount of greenhouse gases and keeps the facing mankind energy and environment dual
Crisis.Energy production structure and Land use systems is pushed to change, promoting the polynary Clean Development of the energy is that China realizes sustainable development
The task of top priority.Bio-natural gas is available, at low cost with its environment-friendly cycle, byproduct as a kind of clean Gas Energy Source
The features such as honest and clean, technology maturation is easily promoted has great application prospect in terms of supplementing China's energy deficiency.
Bio-natural gas, refer to by biomass be transformed with methane combustion gas as main component, refer mainly to lead at present
Cross the biological methane that methane purification obtains.Biogas be organic substance under anaerobic, through microbial fermentation act on and generate
The mixture of multiple gases mainly contains methane and carbon dioxide, and wherein methane accounts for 55%~70%, and carbon dioxide accounts for 30%~
45%.China's Methane Resources very abundant, but Land use systems are more traditional, in addition to a small number of enterprises for obtaining power generation online subsidy,
Predominantly burning boiler, power generation are personal.In recent years, there is more high yield biogas project, daily output methane quantity reaches 10000Nm3~
150000Nm3, it is far longer than enterprise and uses by oneself required tolerance, extra biogas is often passed through boiler imperfect combustion even direct row
It puts, causes environmental pollution and the wasting of resources.Under current energy-saving and emission-reduction sternness trend, methane purification bio-natural gas is high-valued
While using biogas, effectively reduce biogas project because biogas utilization is insufficient empty caused by greenhouse effects, have environmental protection
With energy double benefit.
Conventional method by absorption method, absorption process, membrane separation process, low temperature processing purifying biogas need expensive instrument or
Equipment and higher energy requirement, in purification process a large amount of carbon dioxide with 2%~10% CH4It is discharged into
In atmosphere, the discharge of greenhouse gases is increased, secondary pollution is caused to environment.For the industry for realizing methane purification bio-natural gas
Change production requirement, a kind of methane purification method for developing high-efficiency cleaning is imperative.
Summary of the invention
It is high the invention aims to solve the energy and equipment investment demand during existing methane purification, and there is pollution
The problem of environment, and methane purification membrane bioreactor and its application method are provided.
Methane purification membrane bioreactor, it include water feed apparatus, hydrogen feeder, biogas feeder, reactor,
Circulator and outlet liquid seal device；
The reactor includes reactor body and hollow fiber film assembly, and the hollow fiber film assembly is by doughnut
The both ends of hollow-fibre membrane tow are arranged in film wire beam, membrane component sealing head and membrane module fixing piece composition, membrane component sealing head, utilize
Hollow-fibre membrane tow is fixed in reactor body by membrane module fixing piece by membrane component sealing head, in reactor body
Reactor water inlet is arranged in lower part, and reactor water outlet is arranged on the top of reactor body；
The water feed apparatus by intake pump, water inlet tank and water inlet airbag form, by water inlet line will intake tank with react
The reactor water inlet of device is connected to, and intake pump is arranged on water inlet line, one end of water inlet line is extended into water tank level
Below；Water inlet tank is connected to water inlet airbag by tonifying Qi pipeline, one end of tonifying Qi pipeline is extended into more than water tank level；
The hydrogen feeder includes hydrogen high pressure gas cylinder, hydrogen pressure reducing valve and gas gauge composition, passes through gas
Hydrogen high pressure gas cylinder is connected to by pipeline with hollow-fibre membrane tow, and hydrogen pressure reducing valve and gas pressure are arranged on gas pipeline
Table；
The circulator includes that circulating pump, reflux unit, circulating outlet, reflux unit air inlet, reflux unit go out
The mouth of a river, circulation water inlet and pH electrode；The lower part of reflux unit, reflux dress is arranged in circulating outlet and reflux unit air inlet
The middle part that reflux unit is arranged in water outlet is set, the top of reflux unit is arranged in circulation water inlet, and the setting of pH electrode is flowing back
The top of device, and one end of pH electrode extend to liquid level in reflux unit hereinafter, using pipeline by circulation water inlet with react
Circulating outlet, is connected to by the connection of device water outlet using pipeline with reactor water inlet, is intake in circulating outlet and reactor
Circulating pump is set on the pipeline of mouth connection；
The outlet liquid seal device includes outlet fluid-tight bottle and gas collecting bag, passes through reflux unit water outlet using pipeline
Outlet fluid-tight bottle is connected to reflux unit；Outlet fluid-tight bottle is connected to gas collection bag by tracheae, and one end of tracheae is prolonged
It extends in outlet fluid-tight bottle more than liquid level, liquid outlet is arranged in the lower part of outlet fluid-tight bottle；
The biogas feeder includes biogas high pressure gas cylinder, biogas pressure reducing valve and gas flowmeter composition, utilizes gas
Biogas high pressure gas cylinder is connected to by pipeline by reflux unit air inlet with reflux unit, and biogas pressure reducing valve is arranged on gas pipeline
And gas flowmeter.
The application method of methane purification membrane bioreactor, is specifically realized by the following steps:
One, startup stage: opening intake pump, in the tank that will intake the methane purification biological medium that contains by reactor into
The mouth of a river is injected in reactor body, and reactor body fills rear methane purification biological medium and passes through reactor water outlet and circulation
Water inlet flows into reflux unit, until methane purification biological medium liquid level reaches reflux unit water outlet position in reflux unit
Intake pump is closed when place, then is passed through the nitrogen that purity is 99.99% into reactor body, seals reactor body, then instead
It answers and is inoculated with biogas purifying seed liquor in device main body, the biogas purifying seed liquor and the volume ratio of methane purification biological medium are
1:10, it is clostridium P11 (Clostridium ragsdalei P11) that the biogas, which purifies the bacterial strain in seed liquor,
And the concentration of clostridium P11 is 1.8g/L in biogas purifying seed liquor；It opens hydrogen pressure reducing valve, biogas pressure reducing valve and follows
Ring pump, control loop speed is 65mL/min, Hydrogen Vapor Pressure is 1.25atm and biogas flow be 10mL/min under the conditions of carry out natural pond
Air lift is pure, and raffinate enters in outlet fluid-tight bottle after purification, and biogas slurry is collected in gas collection bag after purification；
Two, continuous running phases: the every operation 12h of methane purification membrane bioreactor closes 1 hydrogen pressure reducing valve, biogas
Pressure reducing valve and circulating pump open 1 intake pump, and methane purification biological medium, and methane purification are injected into reactor body
The additional amount of biological medium is the half of the additional amount of methane purification biological medium in step 1.
The principle of the invention and advantage:
One, reactor is arranged by reactor body lower part by intake pump in the methane purification biological medium in water feed apparatus
Water inlet is pumped into reactor body；Methane purification bacterium in the reaction zone of reactor body mixes under the action of circulating pump
Uniformly, make full use of the hydrogen being dissolved by hollow fiber film assembly by osmosis in liquid, make its with by circulator
In the biogas that is passed through come into full contact with reaction in liquid phase；After fully reacting, water feed apparatus is pumped by intake pump to reactor body
Fresh methane purification biological medium, residual night of fermenting enter outlet fluid-tight bottle by the reflux unit water outlet of circulator,
Middle density of hydrogen realizes that biogas concentration is gentle by biogas pressure reducing valve in liquid by control hydrogen pressure reducing valve and gas gauge
Flowmeter body control.
Two, the present invention realizes methane purification using bioanalysis, effectively prevents expensive equipment investment and energy consumption.
Three, the structure of methane purification membrane bioreactor of the present invention is simple, and workflow is simple, easy to operate, Ke Yigen
Strain stream can be avoided while improving gas effciency to greatest extent by adjusting hydrogen partial pressure according to the purification situation of biogas
It loses, realizes efficient methane purification.
Four, the present invention can make the utilization rate of biogas reach maximization, and the carbon dioxide in biogas passes through microbial action,
Ethyl alcohol, while purifying biogas are generated by electron donor of hydrogen, substantially increases the added value of product.
Five, the present invention obtains the bio-natural gas that purity reaches 93% or more using methane purification membrane bioreactor, together
When alcohol yied reach 1.5g/Ld.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of methane purification membrane bioreactor of the present invention, 1 expression hydrogen high pressure gas cylinder in figure, 2 tables
Show hydrogen pressure reducing valve, 3 indicate reactor body, and 4 indicate hollow-fibre membrane tow, and 5 indicate membrane component sealing head, and 6 indicate reactor
Water outlet, 7 indicate membrane module fixing pieces, 8 indicate reactor water inlets, 9 indicate intake pumps, 10 indicate water inlet tanks, 11 indicate into
Aqueous vapor bag, 12 indicate circulating pump, and 13 indicate reflux unit, and 14 indicate circulating outlet, and 15 indicate reflux unit air inlet, 16 tables
Show reflux unit water outlet, 17 indicate circulation water inlet, and 18 indicate pH electrode, and 19 indicate gas collection bag, and 20 represent gas-liquid
Envelope bottle, 21 expression gas flowmeters, 22 expression biogas pressure reducing valves, 23 expression biogas high pressure gas cylinders, 24 expression magnetic stirring apparatus, 25
Indicate gas gauge.
Specific embodiment
Specific embodiment 1: present embodiment is methane purification membrane bioreactor, it includes water feed apparatus, hydrogen confession
Device of air, biogas feeder, reactor, circulator and outlet liquid seal device；
The reactor includes reactor body 3 and hollow fiber film assembly, and the hollow fiber film assembly is by hollow fibre
It ties up film wire beam 4, membrane component sealing head 5 and membrane module fixing piece 7 to form, the two of hollow-fibre membrane tow 4 are arranged in membrane component sealing head 5
Hollow-fibre membrane tow 4, is fixed in reactor body 3, anti-by end using membrane module fixing piece 7, by membrane component sealing head 5
It answers the lower part of device main body 3 that reactor water inlet 8 is set, reactor water outlet 6 is set on the top of reactor body 3；
The water feed apparatus is made of intake pump 9, water inlet tank 10 and water inlet airbag 11, will water inlet tank 10 by water inlet line
It is connected to the reactor water inlet 8 of reactor, intake pump 9 is set on water inlet line, and one end of water inlet line is extended into water
In tank 10 below liquid level；By tonifying Qi pipeline will intake tank 10 with intake airbag 11 be connected to, one end of tonifying Qi pipeline extend into
In water pot 10 more than liquid level；
The hydrogen feeder includes that hydrogen high pressure gas cylinder 1, hydrogen pressure reducing valve 2 and gas gauge 25 form, and is passed through
Hydrogen high pressure gas cylinder 1 is connected to by gas pipeline with hollow-fibre membrane tow 4, and it is gentle that hydrogen pressure reducing valve 2 is arranged on gas pipeline
Body pressure gauge 25；
The circulator includes circulating pump 12, reflux unit 13, circulating outlet 14, reflux unit air inlet 15, returns
Flow device water outlet 16, circulation water inlet 17 and pH electrode 18；Circulating outlet 14 and the setting of reflux unit air inlet 15 are being returned
The lower part of device 13 is flowed, the middle part of reflux unit 13 is arranged in reflux unit water outlet 16, and the setting of circulation water inlet 17 is flowing back
The top of device 13, the top of reflux unit 13 is arranged in pH electrode 18, and one end of pH electrode 18 extends to reflux unit 13
Interior liquid level hereinafter, circulation water inlet 17 is connected to reactor water outlet 6 using pipeline, using pipeline by circulating outlet 14 with
Reactor water inlet 8 is connected to, and circulating pump 12 is arranged on the pipeline that circulating outlet 14 is connected to reactor water inlet 8；
The outlet liquid seal device includes outlet fluid-tight bottle 20 and gas collecting bag 19, is gone out using pipeline by reflux unit
Outlet fluid-tight bottle 20 is connected to by the mouth of a river 16 with reflux unit 13；Outlet fluid-tight bottle 20 is connected to gas collection bag 19 by tracheae,
And one end of tracheae extends in outlet fluid-tight bottle 20 more than liquid level, liquid outlet is arranged in the lower part of outlet fluid-tight bottle 20；
The biogas feeder includes that biogas high pressure gas cylinder 23, biogas pressure reducing valve 22 and gas flowmeter 21 form, benefit
Biogas high pressure gas cylinder 23 is connected to by reflux unit air inlet 15 with reflux unit 13 with gas pipeline, is set on gas pipeline
Set biogas pressure reducing valve 22 and gas flowmeter 21.
Specific embodiment 2: the difference of present embodiment and specific embodiment one is: the reactor water inlet 8
The two sides of hollow fiber film assembly are set with reactor water outlet 6.Other are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: the biogas mentions
Pure membrane bioreactor further includes magnetic stirring apparatus 24, and reflux unit 13 is arranged on magnetic stirring apparatus 24.Other and specific reality
It is identical to apply mode one or two.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: the water inlet tank
The liquid contained in 10 is methane purification biological medium.Other are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: the biogas mentions
Neat liquid fermentation medium is by NH4Cl、KCl、MgSO4·7H2O、NaCl、KH2PO4、CaCl2·2H2O, yeast powder, trace meter
Element reservoir, vitamin reservoir, NaHCO3, reducing agent reservoir and water is prepared；The methane purification liquid fermentation medium
In by NH4The concentration of Cl is 1.0g/L, and the concentration of KCl is 0.1g/L, MgSO4·7H2The concentration of O is 0.2g/L, the concentration of NaCl
For 0.8g/L, KH2PO4Concentration be 0.1g/L, CaCl2·2H2The concentration of O is 20mg/L, and the concentration of yeast powder is 1g/L, micro-
The concentration for measuring metallic element reservoir is 10mL/L, and the concentration of vitamin reservoir is 10mL/L, NaHCO3Concentration be 2g/L, reduction
The concentration of agent reservoir is 10ml/L；
The minor metallic element reservoir includes nitrilotriacetic acid, MnSO4·H2O、FeSO42NH42·6H2O、CoCl2·
6H2O、ZnSO4·7H2O、CuCl2·2H2O、NiCl2·6H2O、Na2MoO4·2H2O、Na2SeO4And Na2WO4；The micro gold
The concentration for belonging to nitrilotriacetic acid in element reservoir is 2g/L, MnSO4·H2The concentration of O is 1g/L, FeSO42NH42·6H2O's
Concentration is 0.8g/L, CoCl2·6H2The concentration of O is 0.2g/L, ZnSO4·7H2The concentration of O is 0.2mg/L, CuCl2·2H2O's
Concentration is 20mg/L, NiCl2·6H2The concentration of O is 20mg/L, Na2MoO4·2H2The concentration of O is 20mg/L, Na2SeO4It is dense
Degree is 20mg/L, Na2WO4Concentration be 20mg/L composition；
The vitamin reservoir includes biotin, folic acid, hydrochloric acid vitamin B6, thiamine hydrochloride, vitamin B2, it is niacin, general
Sour calcium, vitamin B12, p-aminobenzoic acid and lipoic acid；The concentration of biotin is 2mg/L in the vitamin reservoir, folic acid
Concentration is 2mg/L, hydrochloric acid vitamin B6Concentration be 10mg/L, the concentration of thiamine hydrochloride is 5mg/L, vitamin B2Concentration
For 5mg/L, the concentration of niacin is 5mg/L, and the concentration of calcium pantothenate is 5mg/L, vitamin B12Concentration be 0.1mg/L, to amino
The concentration of benzoic acid is 5mg/L, and the concentration of lipoic acid is 5mg/L；
The reducing agent reservoir includes NaOH, L- cysteine hydrochloride and Na2S·9H2O；NaOH in the reducing agent reservoir
Concentration be 9g/L, the concentration of L- cysteine hydrochloride is 40g/L, Na2S·9H2The concentration of O is 40g/L.
Other are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: the influent gas
The gas contained in bag 11 is nitrogen.Other are identical as specific embodiment one to five.
Specific embodiment 7: present embodiment is the application method of methane purification membrane bioreactor, specifically by with
What lower step was completed:
One, startup stage: opening intake pump 9, and the methane purification biological medium contained in tank 10 of intaking is passed through reaction
Device water inlet 8 injects in reactor body 3, and reactor body 3 fills rear methane purification biological medium and is discharged by reactor
Mouth 6 and circulation water inlet 17 flow into reflux unit 13, until methane purification biological medium liquid level reaches back in reflux unit 13
Intake pump 9 is closed when flowing at 16 position of device water outlet, then the nitrogen that purity is 99.99% is passed through into reactor body 3, it is close
Reactor body 3 is sealed, biogas is then inoculated in reactor body 3 and purifies seed liquor, the biogas purifying seed liquor is mentioned with biogas
The volume ratio of pure biological medium is 1:10, and the biogas purifies the bacterial strain in seed liquor as clostridium P11, and biogas
The concentration for purifying clostridium P11 in seed liquor is 1.8g/L；Open hydrogen pressure reducing valve 2, biogas pressure reducing valve 22 and circulation
Pump 12, control loop speed is 65mL/min, Hydrogen Vapor Pressure is 1.25atm and biogas flow be 10mL/min under the conditions of carry out natural pond
Air lift is pure, and raffinate enters in outlet fluid-tight bottle 20 after purification, and biogas slurry is collected in gas collection bag 19 after purification；
Two, continuous running phases: the every operation 12h of methane purification membrane bioreactor closes 1 hydrogen pressure reducing valve 2, biogas
Pressure reducing valve 22 and circulating pump 12 open 1 intake pump 9, and methane purification biological medium, and natural pond are injected into reactor body 3
The additional amount of the pure biological medium of air lift is the half of the additional amount of methane purification biological medium in step 1.
Specific embodiment 8: the difference of present embodiment and specific embodiment seven is: described in step 1 and two
Methane purification liquid fermentation medium is by NH4Cl、KCl、MgSO4·7H2O、NaCl、KH2PO4、CaCl2·2H2O, yeast powder, micro-
Measure metallic element reservoir, vitamin reservoir, NaHCO3, reducing agent reservoir and water is prepared；The methane purification liquid fermentation
By NH in culture medium4The concentration of Cl is 1.0g/L, and the concentration of KCl is 0.1g/L, MgSO4·7H2The concentration of O is 0.2g/L, NaCl
Concentration be 0.8g/L, KH2PO4Concentration be 0.1g/L, CaCl2·2H2The concentration of O is 20mg/L, and the concentration of yeast powder is
1g/L, the concentration of minor metallic element reservoir are 10mL/L, and the concentration of vitamin reservoir is 10mL/L, NaHCO3Concentration be
2g/L, the concentration of reducing agent reservoir are 10ml/L；
The minor metallic element reservoir includes nitrilotriacetic acid, MnSO4·H2O、FeSO42NH42·6H2O、CoCl2·
6H2O、ZnSO4·7H2O、CuCl2·2H2O、NiCl2·6H2O、Na2MoO4·2H2O、Na2SeO4And Na2WO4；The micro gold
The concentration for belonging to nitrilotriacetic acid in element reservoir is 2g/L, MnSO4·H2The concentration of O is 1g/L, FeSO42NH42·6H2O's
Concentration is 0.8g/L, CoCl2·6H2The concentration of O is 0.2g/L, ZnSO4·7H2The concentration of O is 0.2mg/L, CuCl2·2H2O's
Concentration is 20mg/L, NiCl2·6H2The concentration of O is 20mg/L, Na2MoO4·2H2The concentration of O is 20mg/L, Na2SeO4It is dense
Degree is 20mg/L, Na2WO4Concentration be 20mg/L composition；
The vitamin reservoir includes biotin, folic acid, hydrochloric acid vitamin B6, thiamine hydrochloride, vitamin B2, it is niacin, general
Sour calcium, vitamin B12, p-aminobenzoic acid and lipoic acid；The concentration of biotin is 2mg/L in the vitamin reservoir, folic acid
Concentration is 2mg/L, hydrochloric acid vitamin B6Concentration be 10mg/L, the concentration of thiamine hydrochloride is 5mg/L, vitamin B2Concentration
For 5mg/L, the concentration of niacin is 5mg/L, and the concentration of calcium pantothenate is 5mg/L, vitamin B12Concentration be 0.1mg/L, to amino
The concentration of benzoic acid is 5mg/L, and the concentration of lipoic acid is 5mg/L；
The reducing agent reservoir includes NaOH, L- cysteine hydrochloride and Na2S·9H2O；NaOH in the reducing agent reservoir
Concentration be 9g/L, the concentration of L- cysteine hydrochloride is 40g/L, Na2S·9H2The concentration of O is 40g/L.
Other are identical as specific embodiment seven.
The content of present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several specific embodiments
The purpose of invention also may be implemented in contract sample.
Using following verification experimental verifications effect of the present invention:
Embodiment 1: methane purification membrane bioreactor, it includes water feed apparatus, hydrogen feeder, biogas gas supply dress
It sets, reactor, circulator and outlet liquid seal device；
The reactor includes reactor body 3 and hollow fiber film assembly, and the hollow fiber film assembly is by hollow fibre
It ties up film wire beam 4, membrane component sealing head 5 and membrane module fixing piece 7 to form, the two of hollow-fibre membrane tow 4 are arranged in membrane component sealing head 5
Hollow-fibre membrane tow 4, is fixed in reactor body 3, anti-by end using membrane module fixing piece 7, by membrane component sealing head 5
It answers the lower part of device main body 3 that reactor water inlet 8 is set, reactor water outlet 6 is set on the top of reactor body 3；
The water feed apparatus is made of intake pump 9, water inlet tank 10 and water inlet airbag 11, will water inlet tank 10 by water inlet line
It is connected to the reactor water inlet 8 of reactor, intake pump 9 is set on water inlet line, and one end of water inlet line is extended into water
In tank 10 below liquid level；By tonifying Qi pipeline will intake tank 10 with intake airbag 11 be connected to, one end of tonifying Qi pipeline extend into
In water pot 10 more than liquid level；
The hydrogen feeder includes that hydrogen high pressure gas cylinder 1, hydrogen pressure reducing valve 2 and gas gauge 25 form, and is passed through
Hydrogen high pressure gas cylinder 1 is connected to by gas pipeline with hollow-fibre membrane tow 4, and it is gentle that hydrogen pressure reducing valve 2 is arranged on gas pipeline
Body pressure gauge 25；
The circulator includes circulating pump 12, reflux unit 13, circulating outlet 14, reflux unit air inlet 15, returns
Flow device water outlet 16, circulation water inlet 17 and pH electrode 18；Circulating outlet 14 and the setting of reflux unit air inlet 15 are being returned
The lower part of device 13 is flowed, the middle part of reflux unit 13 is arranged in reflux unit water outlet 16, and the setting of circulation water inlet 17 is flowing back
The top of device 13, the top of reflux unit 13 is arranged in pH electrode 18, and one end of pH electrode 18 extends to reflux unit 13
Interior liquid level hereinafter, circulation water inlet 17 is connected to reactor water outlet 6 using pipeline, using pipeline by circulating outlet 14 with
Reactor water inlet 8 is connected to, and circulating pump 12 is arranged on the pipeline that circulating outlet 14 is connected to reactor water inlet 8；
The outlet liquid seal device includes outlet fluid-tight bottle 20 and gas collecting bag 19, is gone out using pipeline by reflux unit
Outlet fluid-tight bottle 20 is connected to by the mouth of a river 16 with reflux unit 13；Outlet fluid-tight bottle 20 is connected to gas collection bag 19 by tracheae,
And one end of tracheae extends in outlet fluid-tight bottle 20 more than liquid level, liquid outlet is arranged in the lower part of outlet fluid-tight bottle 20；
The biogas feeder includes that biogas high pressure gas cylinder 23, biogas pressure reducing valve 22 and gas flowmeter 21 form, benefit
Biogas high pressure gas cylinder 23 is connected to by reflux unit air inlet 15 with reflux unit 13 with gas pipeline, is set on gas pipeline
Set biogas pressure reducing valve 22 and gas flowmeter 21.
The two sides of hollow fiber film assembly are arranged in the reactor water inlet 8 and reactor water outlet 6.
The methane purification membrane bioreactor further includes magnetic stirring apparatus 24, and reflux unit 13 is arranged in magnetic stirring apparatus
On 24.
The liquid contained in the water inlet tank 10 is methane purification biological medium；The methane purification liquid fermentation and culture
Base is by NH4Cl、KCl、MgSO4·7H2O、NaCl、KH2PO4、CaCl2·2H2O, yeast powder, minor metallic element reservoir, dimension life
Plain reservoir, NaHCO3, reducing agent reservoir and water is prepared；By NH in the methane purification liquid fermentation medium4The concentration of Cl
For 1.0g/L, the concentration of KCl is 0.1g/L, MgSO4·7H2The concentration of O is 0.2g/L, and the concentration of NaCl is 0.8g/L, KH2PO4
Concentration be 0.1g/L, CaCl2·2H2The concentration of O is 20mg/L, and the concentration of yeast powder is 1g/L, minor metallic element reservoir
Concentration is 10mL/L, and the concentration of vitamin reservoir is 10mL/L, NaHCO3Concentration be 2g/L, the concentration of reducing agent reservoir is
10ml/L；The minor metallic element reservoir includes nitrilotriacetic acid, MnSO4·H2O、FeSO42NH42·6H2O、CoCl2·
6H2O、ZnSO4·7H2O、CuCl2·2H2O、NiCl2·6H2O、Na2MoO4·2H2O、Na2SeO4And Na2WO4；The micro gold
The concentration for belonging to nitrilotriacetic acid in element reservoir is 2g/L, MnSO4·H2The concentration of O is 1g/L, FeSO42NH42·6H2O's
Concentration is 0.8g/L, CoCl2·6H2The concentration of O is 0.2g/L, ZnSO4·7H2The concentration of O is 0.2mg/L, CuCl2·2H2O's
Concentration is 20mg/L, NiCl2·6H2The concentration of O is 20mg/L, Na2MoO4·2H2The concentration of O is 20mg/L, Na2SeO4It is dense
Degree is 20mg/L, Na2WO4Concentration be 20mg/L composition；The vitamin reservoir includes biotin, folic acid, hydrochloric acid vitamin
B6, thiamine hydrochloride, vitamin B2, niacin, calcium pantothenate, vitamin B12, p-aminobenzoic acid and lipoic acid；The vitamin storage
The concentration of biotin is 2mg/L in liquid, and the concentration of folic acid is 2mg/L, hydrochloric acid vitamin B6Concentration be 10mg/L, thiamine hydrochloride
The concentration of element is 5mg/L, vitamin B2Concentration be 5mg/L, the concentration of niacin is 5mg/L, and the concentration of calcium pantothenate is 5mg/L,
Vitamin B12Concentration be 0.1mg/L, the concentration of p-aminobenzoic acid is 5mg/L, and the concentration of lipoic acid is 5mg/L；It is described to go back
Former agent reservoir includes NaOH, L- cysteine hydrochloride and Na2S·9H2O；The concentration of NaOH is 9g/L in the reducing agent reservoir,
The concentration of L- cysteine hydrochloride is 40g/L, Na2S·9H2The concentration of O is 40g/L.
The gas contained in the water inlet airbag 11 is nitrogen
Embodiment 2: the application method of methane purification membrane bioreactor described in embodiment 1, it is specifically complete according to the following steps
At:
One, startup stage: opening intake pump 9, and the methane purification biological medium contained in tank 10 of intaking is passed through reaction
Device water inlet 8 injects in reactor body 3, and reactor body 3 fills rear methane purification biological medium and is discharged by reactor
Mouth 6 and circulation water inlet 17 flow into reflux unit 13, until methane purification biological medium liquid level reaches back in reflux unit 13
Intake pump 9 is closed when flowing at 16 position of device water outlet, then the nitrogen that purity is 99.99% is passed through into reactor body 3, it is close
Reactor body 3 is sealed, biogas is then inoculated in reactor body 3 and purifies seed liquor, the biogas purifying seed liquor is mentioned with biogas
The volume ratio of pure biological medium is 1:10, and the biogas purifies the bacterial strain in seed liquor as clostridium P11, and biogas
The concentration for purifying clostridium P11 in seed liquor is 1.8g/L；Open hydrogen pressure reducing valve 2, biogas pressure reducing valve 22 and circulation
Pump 12, control loop speed is 65mL/min, Hydrogen Vapor Pressure is 1.25atm and biogas flow be 10mL/min under the conditions of carry out natural pond
Air lift is pure, and raffinate enters in outlet fluid-tight bottle 20 after purification, and biogas slurry is collected in gas collection bag 19 after purification；
Two, continuous running phases: the every operation 12h of methane purification membrane bioreactor closes 1 hydrogen pressure reducing valve 2, biogas
Pressure reducing valve 22 and circulating pump 12 open 1 intake pump 9, and methane purification biological medium, and natural pond are injected into reactor body 3
The additional amount of the pure biological medium of air lift is the half of the additional amount of methane purification biological medium in step 1.
The biogas after purification collected in the gas collection bag 19 of embodiment 2 is detected it is found that the purity of biogas is
93.2% or more；Liquid in the outlet fluid-tight bottle 20 of embodiment 2 is detected, it is known that the alcohol yied of embodiment 2 is
1.56g/L·d。
Claims (8)
1. methane purification membrane bioreactor, it is characterised in that methane purification membrane bioreactor includes water feed apparatus, hydrogen confession
Device of air, biogas feeder, reactor, circulator and outlet liquid seal device；
The reactor includes reactor body (3) and hollow fiber film assembly, and the hollow fiber film assembly is by doughnut
Film wire beam (4), membrane component sealing head (5) and membrane module fixing piece (7) composition, membrane component sealing head (5) are arranged in hollow fiber film thread
Hollow-fibre membrane tow (4) is fixed on instead by the both ends of beam (4) using membrane module fixing piece (7), by membrane component sealing head (5)
It answers in device main body (3), reactor water inlet (8) is set in the lower part of reactor body (3), on the top of reactor body (3)
It is arranged reactor water outlet (6)；
The water feed apparatus by intake pump (9), water inlet tank (10) and intake airbag (11) form, will be intake tank by water inlet line
(10) it is connected to the reactor water inlet (8) of reactor, intake pump (9) is set on water inlet line, one end of water inlet line is prolonged
It extends into below water tank (10) interior liquid level；Water inlet tank (10) is connected to water inlet airbag (11) by tonifying Qi pipeline, tonifying Qi pipeline
One end extend into more than water tank (10) interior liquid level；
The hydrogen feeder includes hydrogen high pressure gas cylinder (1), hydrogen pressure reducing valve (2) and gas gauge (25) composition, is led to
It crosses gas pipeline and is connected to hydrogen high pressure gas cylinder (1) with hollow-fibre membrane tow (4), hydrogen pressure reducing valve is set on gas pipeline
(2) and gas gauge (25)；
The circulator includes circulating pump (12), reflux unit (13), circulating outlet (14), reflux unit air inlet
(15), reflux unit water outlet (16), circulation water inlet (17) and pH electrode (18)；Circulating outlet (14) and reflux unit into
In the lower part of reflux unit (13), reflux unit water outlet (16) is arranged at the middle part of reflux unit (13) for port (15) setting,
Circulation water inlet (17) setting is arranged in the top of reflux unit (13), pH electrode (18) at the top of reflux unit (13), and
One end of pH electrode (18) extends to reflux unit (13) interior liquid level hereinafter, using pipeline by circulation water inlet (17) and reactor
Circulating outlet (14), is connected to, in circulating outlet (14) by water outlet (6) connection using pipeline with reactor water inlet (8)
Circulating pump (12) are set on the pipeline being connected to reactor water inlet (8)；
The outlet liquid seal device includes outlet fluid-tight bottle (20) and gas collecting bag (19), is gone out using pipeline by reflux unit
Outlet fluid-tight bottle (20) is connected to by the mouth of a river (16) with reflux unit (13)；Outlet fluid-tight bottle (20) passes through with gas collection bag (19)
Tracheae connection, and one end of tracheae extends to outlet fluid-tight bottle (20) interior liquid level or more, the lower part setting of outlet fluid-tight bottle (20)
Liquid outlet；
The biogas feeder includes that biogas high pressure gas cylinder (23), biogas pressure reducing valve (22) and gas flowmeter (21) form,
Biogas high pressure gas cylinder (23) is connected to reflux unit (13) by reflux unit air inlet (15) using gas pipeline, in gas
Biogas pressure reducing valve (22) and gas flowmeter (21) are set on pipeline.
2. methane purification membrane bioreactor according to claim 1, it is characterised in that the reactor water inlet (8) and
The two sides of hollow fiber film assembly are arranged in reactor water outlet (6).
3. methane purification membrane bioreactor according to claim 1, it is characterised in that the methane purification membrane bioreaction
Answering device further includes magnetic stirring apparatus (24), and reflux unit (13) is arranged on magnetic stirring apparatus (24).
4. methane purification membrane bioreactor according to claim 1, it is characterised in that contained in the water inlet tank (10)
Liquid be methane purification biological medium.
5. methane purification membrane bioreactor according to claim 4, it is characterised in that the methane purification liquid fermentation
Culture medium is by NH4Cl、KCl、MgSO4·7H2O、NaCl、KH2PO4、CaCl2·2H2O, yeast powder, minor metallic element reservoir,
Vitamin reservoir, NaHCO3, reducing agent reservoir and water is prepared；By NH in the methane purification liquid fermentation medium4Cl's
Concentration is 1.0g/L, and the concentration of KCl is 0.1g/L, MgSO4·7H2The concentration of O is 0.2g/L, and the concentration of NaCl is 0.8g/L,
KH2PO4Concentration be 0.1g/L, CaCl2·2H2The concentration of O is 20mg/L, and the concentration of yeast powder is 1g/L, minor metallic element
The concentration of reservoir is 10mL/L, and the concentration of vitamin reservoir is 10mL/L, NaHCO3Concentration be 2g/L, reducing agent reservoir it is dense
Degree is 10ml/L；
The minor metallic element reservoir includes nitrilotriacetic acid, MnSO4·H2O、Fe(SO4)2(NH4)2·6H2O、CoCl2·
6H2O、ZnSO4·7H2O、CuCl2·2H2O、NiCl2·6H2O、Na2MoO4·2H2O、Na2SeO4And Na2WO4；The micro gold
The concentration for belonging to nitrilotriacetic acid in element reservoir is 2g/L, MnSO4·H2The concentration of O is 1g/L, Fe (SO4)2(NH4)2·
6H2The concentration of O is 0.8g/L, CoCl2·6H2The concentration of O is 0.2g/L, ZnSO4·7H2The concentration of O is 0.2mg/L, CuCl2·
2H2The concentration of O is 20mg/L, NiCl2·6H2The concentration of O is 20mg/L, Na2MoO4·2H2The concentration of O is 20mg/L, Na2SeO4
Concentration be 20mg/L, Na2WO4Concentration be 20mg/L composition；
The vitamin reservoir includes biotin, folic acid, hydrochloric acid vitamin B6, thiamine hydrochloride, vitamin B2, niacin, pantothenic acid
Calcium, vitamin B12, p-aminobenzoic acid and lipoic acid；In the vitamin reservoir concentration of biotin be 2mg/L, folic acid it is dense
Degree is 2mg/L, hydrochloric acid vitamin B6Concentration be 10mg/L, the concentration of thiamine hydrochloride is 5mg/L, vitamin B2Concentration be
5mg/L, the concentration of niacin are 5mg/L, and the concentration of calcium pantothenate is 5mg/L, vitamin B12Concentration be 0.1mg/L, p-aminophenyl
The concentration of formic acid is 5mg/L, and the concentration of lipoic acid is 5mg/L；
The reducing agent reservoir includes NaOH, L- cysteine hydrochloride and Na2S·9H2O；NaOH's is dense in the reducing agent reservoir
Degree is 9g/L, and the concentration of L- cysteine hydrochloride is 40g/L, Na2S·9H2The concentration of O is 40g/L.
6. methane purification membrane bioreactor according to claim 1, it is characterised in that contained in the water inlet airbag (11)
The gas of dress is nitrogen.
7. the application method of methane purification membrane bioreactor, it is characterised in that it is completed by the following steps:
One, startup stage: opening intake pump (9), and tank (10) the interior methane purification biological medium contained that will intake passes through reaction
Device water inlet (8) injects in reactor body (3), and reactor body (3) fills rear methane purification biological medium and passes through reaction
Device water outlet (6) and circulation water inlet (17) flow into reflux unit (13), until the interior methane purification biology training of reflux unit (13)
It supports base fluid face and closes intake pump (9) when reaching at reflux unit water outlet (16) position, then be passed through in reactor body (3) pure
The nitrogen that degree is 99.99% seals reactor body (3), and then inoculation biogas purifies seed liquor, institute in reactor body (3)
The volume ratio for stating biogas purifying seed liquor and methane purification biological medium is 1:10, the bacterial strain in the biogas purifying seed liquor
For clostridium P11, and the concentration of clostridium P11 is 1.8g/L in biogas purifying seed liquor；Hydrogen is opened to subtract
Pressure valve (2), biogas pressure reducing valve (22) and circulating pump (12), control loop speed is 65mL/min, Hydrogen Vapor Pressure be 1.25atm and
Biogas flow carries out methane purification under the conditions of being 10mL/min, and raffinate enters in outlet fluid-tight bottle (20) after purification, natural pond after purification
Liquid is collected in gas collection bag (19)；
Two, continuous running phases: the every operation 12h of methane purification membrane bioreactor closes 1 hydrogen pressure reducing valve (2), biogas and subtracts
Pressure valve (22) and circulating pump (12) open 1 intake pump (9), to injection methane purification biological culture in reactor body (3)
Base, and the additional amount of methane purification biological medium be step 1 in methane purification biological medium additional amount two/
One.
8. the application method of methane purification membrane bioreactor according to claim 7, it is characterised in that step 1 and two
Described in methane purification liquid fermentation medium by NH4Cl、KCl、MgSO4·7H2O、NaCl、KH2PO4、CaCl2·2H2O, ferment
Female powder, minor metallic element reservoir, vitamin reservoir, NaHCO3, reducing agent reservoir and water is prepared；The methane purification liquid
By NH in body fermentation medium4The concentration of Cl is 1.0g/L, and the concentration of KCl is 0.1g/L, MgSO4·7H2The concentration of O is 0.2g/
The concentration of L, NaCl are 0.8g/L, KH2PO4Concentration be 0.1g/L, CaCl2·2H2The concentration of O be 20mg/L, yeast powder it is dense
Degree is 1g/L, and the concentration of minor metallic element reservoir is 10mL/L, and the concentration of vitamin reservoir is 10mL/L, NaHCO3Concentration
For 2g/L, the concentration of reducing agent reservoir is 10ml/L；
The minor metallic element reservoir includes nitrilotriacetic acid, MnSO4·H2O、Fe(SO4)2(NH4)2·6H2O、CoCl2·
6H2O、ZnSO4·7H2O、CuCl2·2H2O、NiCl2·6H2O、Na2MoO4·2H2O、Na2SeO4And Na2WO4；The micro gold
The concentration for belonging to nitrilotriacetic acid in element reservoir is 2g/L, MnSO4·H2The concentration of O is 1g/L, Fe (SO4)2(NH4)2·
6H2The concentration of O is 0.8g/L, CoCl2·6H2The concentration of O is 0.2g/L, ZnSO4·7H2The concentration of O is 0.2mg/L, CuCl2·
2H2The concentration of O is 20mg/L, NiCl2·6H2The concentration of O is 20mg/L, Na2MoO4·2H2The concentration of O is 20mg/L, Na2SeO4
Concentration be 20mg/L, Na2WO4Concentration be 20mg/L composition；
The vitamin reservoir includes biotin, folic acid, hydrochloric acid vitamin B6, thiamine hydrochloride, vitamin B2, niacin, pantothenic acid
Calcium, vitamin B12, p-aminobenzoic acid and lipoic acid；In the vitamin reservoir concentration of biotin be 2mg/L, folic acid it is dense
Degree is 2mg/L, hydrochloric acid vitamin B6Concentration be 10mg/L, the concentration of thiamine hydrochloride is 5mg/L, vitamin B2Concentration be
5mg/L, the concentration of niacin are 5mg/L, and the concentration of calcium pantothenate is 5mg/L, vitamin B12Concentration be 0.1mg/L, p-aminophenyl
The concentration of formic acid is 5mg/L, and the concentration of lipoic acid is 5mg/L；
The reducing agent reservoir includes NaOH, L- cysteine hydrochloride and Na2S·9H2O；NaOH's is dense in the reducing agent reservoir
Degree is 9g/L, and the concentration of L- cysteine hydrochloride is 40g/L, Na2S·9H2The concentration of O is 40g/L.
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